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Title: Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides
Authors: Niemeyer, J.
Kelly, M. J.
Riddlestone, I. M.
Vidović, Dragoslav
Aldridge, S.
Keywords: DRNTU::Science::Chemistry::Organic chemistry::Carbanions
Issue Date: 2015
Source: Niemeyer, J., Kelly, M. J., Riddlestone, I. M., Vidovic, D., & Aldridge, S. (2015). Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides. Dalton Trans., 44(25), 11294-11305.
Series/Report no.: Dalton Trans.
Abstract: The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM[double bond, length as m-dash]B[double bond, length as m-dash]N[double bond, length as m-dash]CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines – a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)]+[BArX4]− (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; ArX = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M[double bond, length as m-dash]B metathesis reactivity with a carbodiimide, and results in Fe[double bond, length as m-dash]B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)]+[BArCl4]− (R = iPr/Cy, 16/17).
ISSN: 1477-9226
DOI: 10.1039/C5DT00131E
Rights: © 2015 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

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